Background technology
Poly carboxylic acid series water reducer, because having high water reducing rate, high-collapse-retentivity, high enhancing and high resistance to premium properties of waiting so long, is applied in concrete works more and more widely.But, a large amount of case histories and research show, compared with the water reducers such as naphthalene system, melamine series and amido sulfoacid series, poly carboxylic acid series water reducer is more responsive to the silt content of aggregate, main manifestations be poly carboxylic acid series water reducer diminishing dispersive ability degradation, protect and to collapse weak effect, cause maturing intensity reduction etc.In high aggregate silt content situation, the simple volume improving poly carboxylic acid series water reducer can not solve the problem such as water-reducing rate, slump retaining, and this is also affect the major reason of poly carboxylic acid series water reducer in ready mixed concrete industry large-scale promotion.
In ready mixed concrete actual production, when the silt content in aggregate be above standard regulation and obviously have influence on concrete quality time, general employing is rinsed as conventional solution, but rinse the good grating of the sand that pollutes the environment, damages, be unfavorable for effectively controlling concrete water cement ratio, thus rinse not economical rationality under many circumstances.National standard JGJ52-2006 defines the authentication method of mud in aggregate and limits its content.There are some researches show and can be improved the side effect that aggregate brings to concrete containing mud by compounded technology.Such as CN101798197A uses composite way to solve the high problem of aggregate silt content, but the collocation of natural zeolite powder and water reducer can bring the inconvenience in use, and the membership that adds of retardant causes concrete retarding, brings the impact of construction and intensity aspect.CN102358763A has prepared a kind of admixture suppressing side effect of clay, and belong to a kind of small-molecule modulators in essence, water-reducing rate own is limited, also needs to carry out composite with water reducer in application.But preparation method not only can bring cost significantly to improve when solving aggregate silt content problem, and the problems such as the consistency of organic-inorganic component, package stability also can occur.CN102617811A discloses the preparation method of the anti-mud agent of a kind of amphoteric ethylene polymer concrete, adopt the method for first esterification post polymerization, introduce cation group in the molecular structure, obtain a kind of anti-mud agent, but the method esterification and polymerization temperature higher, be unfavorable for industrial applications, more owing to introducing the vinyl monomer containing chlorion, may steel bar corrosion be caused.
Therefore, from of the poly carboxylic acid series water reducer molecular structure itself, by introducing functional group, develop a kind of be applicable to high containing mud aggregate, reaction process simply, the poly carboxylic acid series water reducer of not chloride ion-containing, for poly carboxylic acid series water reducer wideling popularize and application in ready mixed concrete industry, tool has very important significance.
Summary of the invention
The object of the present invention is to provide a kind of anti-chamotte mould poly carboxylic acid series water reducer and preparation method thereof.This kind of poly carboxylic acid series water reducer is adopted when aggregate silt content is higher, aggregate silt content in ready mixed concrete can be avoided to the detrimentally affect of poly carboxylic acid series water reducer, under the prerequisite not improving poly carboxylic acid series water reducer volume, to solve the problems such as concrete diminishing is inadequate, slump-loss large, low strength.
Present invention also offers the preparation method of above-mentioned anti-chamotte mould poly carboxylic acid series water reducer, comprise the following steps:
(1) preparation of quaternary ammonium salt oligopolymer: add a certain amount of epoxy bromopropane in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed, using lower alcohol, water as mixed solvent; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 20 ~ 50 DEG C under nitrogen atmosphere, then in 0.5 ~ 3 hour, slowly dripping a certain amount of tertiary amine compounds aqueous solution, and stirring at low speed; Add acid regulator regulation system pH value 1 ~ 2, add composite initiator, be then warming up to 50 ~ 80 DEG C of reactions and stop for 5 ~ 8 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the quaternary ammonium salt oligopolymer prepared by a certain amount of step (1), isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide), Amino Trimethylene Phosphonic Acid and water in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 30 ~ 70 DEG C under agitation, add initiator; Then unsaturated monocarboxylic acid and derivatives monomer, chain-transfer agent and water are made into mixing solutions, dripped off with constant speed in 2 ~ 5 hours, and at 30 ~ 70 DEG C constant temperature 1 ~ 2 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
A kind of anti-chamotte mould poly carboxylic acid series water reducer and preparation method thereof, is characterized in that, comprise the following steps:
(1) preparation of quaternary ammonium salt oligopolymer: add a certain amount of epoxy bromopropane in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed, using lower alcohol, water as mixed solvent; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, then in 0.5 ~ 1.5 hour, slowly dripping a certain amount of tertiary amine compounds aqueous solution, and stirring at low speed; Add acid regulator regulation system pH value 1 ~ 2, add composite initiator, be then warming up to 60 ~ 70 DEG C of reactions and stop for 5 ~ 8 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the quaternary ammonium salt oligopolymer prepared by a certain amount of step (1), isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide), Amino Trimethylene Phosphonic Acid and water in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 45 ~ 60 DEG C under agitation, add initiator; Then unsaturated monocarboxylic acid and derivatives monomer, chain-transfer agent and water are made into mixing solutions, dripped off with constant speed in 3 hours, and at 45 ~ 60 DEG C constant temperature 1 ~ 2 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
The described lower alcohol as mixed solvent is the mixture of one or more in methyl alcohol, ethanol, Virahol, isopropylcarbinol.
Described tertiary amine compounds is the one in dimethylamine, diethylamine, Trimethylamine 99, triethylamine, and the mol ratio of tertiary amine compounds and epoxy bromopropane is 1.1:1 ~ 1.4:1.
The described material as acid regulator is the one in phosphoric acid, the vitriol oil, hydrofluoric acid.
Described composite initiator adopts persulphate as oxygenant, comprises ammonium persulphate, Potassium Persulphate and Sodium Persulfate, adopts sulphite, hydrosulphite or hypophosphite as reductive agent.
Described unsaturated monocarboxylic acid and derivative thereof are the mixtures of one or more in (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) acrylamide.
Initiator in described step (2) is ammonium persulphate, and more excellent consumption is 0.4 ~ 1.5% of reaction monomers gross weight, and more excellent consumption is 0.7 ~ 1.0% of reaction monomers gross weight.
Described chain-transfer agent is the one in thin base ethanol, Thiovanic acid, thiohydracrylic acid, and more excellent consumption is 0.1 ~ 1.0% of reaction monomers gross weight, and more excellent consumption is 0.2 ~ 0.5% of reaction monomers gross weight.
Beneficial effect of the present invention:
Owing to containing anti-stick soil matrix group in molecular structure, effectively can shield the absorption of clay to poly carboxylic acid series water reducer, make the carboxylic acid ion in molecular structure and polyether lateral chain play the effect of absorption cement and dispersion cement respectively, thus ensured that the diminishing of poly carboxylic acid series water reducer protects the effect of collapsing; Due to the existence of anti-mud component, can strengthen the sterically hindered effect of polyether lateral chain, improve water-reducing rate, therefore product application of the present invention is not when containing pureed condition, and water-reducing rate is higher than general poly carboxylic acid series water reducer; The present invention adopts normal pressure to produce, and equipment requirements is low, easy to operate, is conducive to suitability for industrialized production, and not chloride ion-containing in product, to the reinforcing bar non-corroding harm in concrete.
Embodiment
Describe embodiments of the present invention in detail with specific embodiment below, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
Embodiment 1:
(1) preparation of quaternary ammonium salt oligopolymer: add the epoxy bromopropane of 137 weight parts, the ethanol of 400 weight parts and the water of 98.2 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, in 1 hour, then slowly dripping the trimethylamine solution (30%) of 236 weight parts, and stirring at low speed; Add the phosphoric acid regulation system pH value 1 ~ 2 of 23 weight parts, add the ammonium persulphate of 0.8 weight part, the sodium hypophosphite of 5 weight parts and the composite initiator solution of 100 weight parts waters composition, be then warming up to 65 ~ 70 DEG C of reactions and stop for 5.5 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer PQA-1.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the PQA-1 of 19.2 weight parts, the isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide) of 400 weight parts, the Amino Trimethylene Phosphonic Acid of 24.8 weight parts and the water of 300 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 50 DEG C under agitation, add the ammonium persulphate of 4.4 weight parts; Then the thiohydracrylic acid of the vinylformic acid of 44.2 weight parts, 1.5 weight parts and the water of 180.5 weight parts are made into mixing solutions, dripped off with constant speed in 3 hours, and at 50 DEG C constant temperature 1 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution of 25.4 weight parts and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
Embodiment 2:
(1) preparation of quaternary ammonium salt oligopolymer: add the epoxy bromopropane of 137 weight parts, the Virahol of 200 weight parts and the water of 165.2 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, in 1.5 hours, then slowly dripping the triethylamine solution (30%) of 370 weight parts, and stirring at low speed; Add the phosphoric acid regulation system pH value 1 ~ 2 of 21 weight parts, add the Potassium Persulphate of 0.8 weight part, the sodium bisulfite of 6 weight parts and the composite initiator solution of 100 weight parts waters composition, be then warming up to 65 ~ 70 DEG C of reactions and stop for 7 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer PQA-2.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the PQA-2 of 18.6 weight parts, the isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide) of 390 weight parts, the Amino Trimethylene Phosphonic Acid of 21 weight parts and the water of 300 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 45 DEG C under agitation, add the ammonium persulphate of 3.8 weight parts; Then the water of the Hydroxyethyl acrylate of the vinylformic acid of 22.8 weight parts, 36.5 weight parts, the mercaptoethanol of 1.4 weight parts and 182.1 weight parts is made into mixing solutions, dripped off with constant speed in 3 hours, and at 45 DEG C constant temperature 1 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution of 23.8 weight parts and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
Embodiment 3:
(1) preparation of quaternary ammonium salt oligopolymer: add the epoxy bromopropane of 137 weight parts, the methyl alcohol of 340 weight parts and the water of 112 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, in 1.5 hours, then slowly dripping the diethylamine solution (30%) of 292 weight parts, and stirring at low speed; Add the vitriol oil regulation system pH value 1 ~ 2 of 11 weight parts, add the Sodium Persulfate of 1 weight part, the S-WAT of 7 weight parts and the composite initiator solution of 100 weight parts waters composition, be then warming up to 65 ~ 70 DEG C of reactions and stop for 6 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer PQA-3.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the PQA-3 of 22.5 weight parts, the isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide) of 375 weight parts, the Amino Trimethylene Phosphonic Acid of 16.5 weight parts and the water of 300 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 60 DEG C under agitation, add the ammonium persulphate of 4.4 weight parts; Then the water of the Propylene glycol monoacrylate of the acrylamide of 28.5 weight parts, 42 weight parts, the Thiovanic acid of 2.4 weight parts and 180.2 weight parts is made into mixing solutions, dripped off with constant speed in 3 hours, and at 60 DEG C constant temperature 1 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution of 26.5 weight parts and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
Embodiment 4:
(1) preparation of quaternary ammonium salt oligopolymer: add the epoxy bromopropane of 137 weight parts, the ethanol of 380 weight parts and the water of 143.2 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, in 0.5 hour, then slowly dripping the dimethylamine solution (30%) of 195 weight parts, and stirring at low speed; Add the hydrofluoric acid regulation system pH value 1 ~ 2 of 38 weight parts, add the ammonium persulphate of 0.8 weight part, the sodium bisulfite of 6 weight parts and the composite initiator solution of 100 weight parts waters composition, be then warming up to 65 ~ 70 DEG C of reactions and stop for 8 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer PQA-4.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the PQA-4 of 16.2 weight parts, the isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide) of 405 weight parts, the Amino Trimethylene Phosphonic Acid of 12.5 weight parts and the water of 300 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 50 DEG C under agitation, add the ammonium persulphate of 4.4 weight parts; Then the water of the methyl acrylate of the vinylformic acid of 21.6 weight parts, 34.4 weight parts, the mercaptoethanol of 1.5 weight parts and 184.4 weight parts is made into mixing solutions, dripped off with constant speed in 3 hours, and at 50 DEG C constant temperature 1 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution of 20 weight parts and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
Embodiment 5:
(1) preparation of quaternary ammonium salt oligopolymer: add the epoxy bromopropane of 137 weight parts, the isopropylcarbinol of 315 weight parts and the water of 154 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, nitrogen ingress pipe, reflux exchanger are housed; Under agitation nitrogen displacement carried out to reaction vessel and be heated to 30 ~ 35 DEG C under nitrogen atmosphere, in 1 hour, then slowly dripping the trimethylamine solution (30%) of 265 weight parts, and stirring at low speed; Add the hydrofluoric acid regulation system pH value 1 ~ 2 of 23 weight parts, add the Sodium Persulfate of 1 weight part, the sodium hypophosphite of 5 weight parts and the composite initiator solution of 100 weight parts waters composition, be then warming up to 65 ~ 70 DEG C of reactions and stop for 7 hours.Reaction solution carries out underpressure distillation in 70kPa vacuum tightness, at 90 DEG C, obtains faint yellow thick quaternary ammonium salt oligopolymer PQA-5.
(2) preparation of anti-chamotte mould poly carboxylic acid series water reducer: add the PQA-5 of 26 weight parts, the isopentenol polyoxyethylene ether (the average addition mole number 54 of ethylene oxide) of 385 weight parts, the Amino Trimethylene Phosphonic Acid of 21.5 weight parts and the water of 300 weight parts in the four-hole boiling flask that thermometer, agitator, constant pressure funnel, reflux exchanger are housed, be heated to 45 DEG C under agitation, add the ammonium persulphate of 4.5 weight parts; Then the water of the Propylene glycol monoacrylate of the vinylformic acid of 25.2 weight parts, 39 weight parts, the thiohydracrylic acid of 1.5 weight parts and 175.8 weight parts is made into mixing solutions, dripped off with constant speed in 3 hours, and at 45 DEG C constant temperature 1 hour, complete polyreaction.Then, after being cooled to 30 DEG C, being neutralized to pH value 6 ~ 7 with 30% aqueous sodium hydroxide solution of 21.5 weight parts and obtaining containing anti-chamotte mould poly carboxylic acid series water reducer of the present invention.
Application Example 1:
Flowing degree of net paste of cement, with reference to standard GB/T/T8077-2008 " Methods for testing uniformity of concrete admixture ", presses the cement of inner blending method replacement respective quality with different sodium bentonites; Sodium bentonite is that Nanjing Tang Shan wilkinite company limited produces, and three kinds of cement are reference cement, the conch P.O42.5 cement of Chinese cement Co., Ltd., Factory product and the fort P.O42.5 cement of Huaxin Concrete Co., Ltd's product respectively; Commercial ester class poly carboxylic acid PCA-M and ethers poly carboxylic acid PCA-T selected by the poly carboxylic acid series water reducer sample of contrast, and the volume of water reducer is that 0.2%(is to roll over the weight of cement admittedly for benchmark), test-results is in table 1.
Paste flowing degree and loss contrast (mm) under the different silt content of table 1
Application Example 2:
Assess the anti-chamotte mould poly carboxylic acid series water reducer synthesized by the present invention by the concrete slump and slump-loss mixing poly carboxylic acid series water reducer in investigation fine aggregate during different silt content, the relevant criterion with reference to GB8076-2008 performs.Test cement adopts reference cement; Test sand is river sand, and fineness modulus 2.7 cleans and dries; Stone is rubble, and 5 ~ 20mm continuous grading is cleaned and dries; Adjust the silt content of fine aggregate by the river sand of inner blending method replacement respective quality with different sodium bentonites; Concrete mix is in table 2, and concrete test the results are shown in Table 3.
Table 2 concrete mix (kg/m
3)
Cement |
Sand |
Stone |
Water |
Water reducer |
360 |
818 |
1062 |
180 |
1.6 |
The fresh concrete slump and loss contrast (mm) under the different silt content of table 3
As can be seen from the contrast of flowing degree of net paste of cement and fresh concrete workability, anti-chamotte mould poly carboxylic acid series water reducer of the present invention can effectively resist bentonitic disadvantageous effect, and containing or situation not argillaceous under, water-reducing property is all higher than commercially available contrast poly carboxylic acid series water reducer sample.
Although the present invention is described by embodiment, embodiment is not used for limiting the present invention.Those skilled in the art in the scope of spirit of the present invention, can make various distortion and improvement, the adjustment of such as component proportions or time range, and the effect after this adjustment is predictable, so it is equally within protection scope of the present invention.Therefore the protection domain that protection scope of the present invention should define with the technical characteristic that the claim of the application is identical or equivalent is as the criterion.